Morphological characterization of attapulgite/poly(methyl methacrylate) particles prepared by soapless emulsion polymerization

BACKGROUND: The synthesis of core–shell inorganic/polymer nanocomposites, in which the polymer shell determines the chemical properties and the interaction with the environment, whereas their physical properties are governed by both the size and shape of the inorganic core and the surrounding organic layer, is an area of increasing research activity. RESULTS: Core–shell and bead–string shaped attapulgite/poly(methyl methacrylate) (ATP/PMMA) nanocomposite particles were prepared by soapless emulsion polymerization in an aqueous suspension of attapulgite organically modified with cetyltrimethylammonium bromide. CONCLUSION: Transmission electron microscopy analysis results showed that the amounts of the monomer added had no influence on the morphologies of the ATP/PMMA particles. The morphologies only depended on the length/diameter ratio of the attapulgite fibrillar single crystal used. Long ATP needles formed the bead–string structure while short ATP needles formed the core–shell structure. Copyright © 2007 Society of Chemical Industry     

Sintering behavior of poly(methyl methacrylate) particles

The sintering behavior of poly(methyl methacrylate) (PMMA) particles was studied by photographic, means and mechanical testing. Interpretation of the data gives the sequence of events taking place during high temperature sintering (without pre-compaction). Optical observations, show essentially two main sintering regions while mechanical studies also give an intermediate transition zone separating these two regions. It is suggested that the flow mechanisms involved in the sintering process are viscoelastfc flow in the lower temperature range and shorter times and non-Newtonian viscous flow in the higher temperature range and longer times.     

Preparation of micron-size monodisperse poly(methyl methacrylate) particles using poly(2-oxazoline) macromonomer

Micron-size monodisperse poly(methyl methacrylate) particles were prepared by dispersion copolymerization of methyl methacrylate with a hydrophilic poly(2-oxazoline) macromonomer in an aqueous methanol solution. The macromonomer acted as a comonomer as well as a stabilizer. As the macromonomer concentration increased, the diameter of the particles decreased. The macromonomer with higher molecular weight, or with more hydrophilic nature, stabilized the particles more effectively The diameter of the particles was dependent on the initiator concentration. Under the conditions giving monodisperse particles, the particle volume increased linearly with the yield of the particles and the particle number was almost constant during the copolymerization. From ESCA analysis of the particle surface, poly(2-oxazoline) chains were enriched on the surface.     

Emulsion polymerization of methyl methacrylate using poly(methyl methacrylate-co-2-hydroxypropyl methacrylate)-graft-polyoxyethylene as the stabilizer

This study involved the use of an amphipathic graft copolymer, poly(methyl methacrylate-co-2-hydroxypropyl methacrylate)–graft–polyoxyethylene, as a stabilizer in the emulsion polymerization of methyl methacrylate. The stabilizing effectiveness of this graft copolymer was studied as a function of its chemical structure. It was found that the stabilizing effectiveness of the graft copolymer was independent of the molecular weight of the backbone within the investigated range of 4 × 10³ g/mol to 2 × 10⁴ g/mol. In all cases, stable emulsion polymerizations of methyl methacrylate were observed. Effective stabilization also occurred when the graft moieties possessed a molecular weight of either 2 × 10³ g/mol or 5 × 10³ g/mol. However, the stabilizing effectiveness was found to be dependent on the amount of polyoxyethylene (POE) contained in the graft copolymer. In this case, graft copolymers possessing 67% by weight POE were poor stabilizers, but ones with 85% POE were very good stabilizers. Moreover, the graft copolymers were found to be superior stabilizers as compared to POE homopolymers.     

Morphology of polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) composite particles

Polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) (PS/PS-b-PMMA/PMMA) composite particles were prepared by releasing toluene from PS/PS-b-PMMA/PMMA/toluene droplets dispersed in a sodium dodecyl sulfate aqueous solution. The morphology of the composite particles was affected by release rate of toluene, the molecular weight of PS-b-PMMA, droplet size, and polymer composition. ‘Onion-like’ multilayered composite particles were prepared from toluene droplets of PS-b-PMMA and of PS/PS-b-PMMA/PMMA, in which the weights of PS and PMMA were the same. The layer thicknesses of the latter multilayered composite particles increased with an increase in the amount of the homopolymers. PS-b-PMMA/PS composite particles had a sea-islands structure, in which PMMA domains were dispersed in a PS matrix. On the other hand, PS-b-PMMA/PMMA composite particles had a cylinder-like structure consisting of a PMMA matrix and PS domains.     

Graphene based composites prepared through exfoliation of graphite platelets in methyl methacrylate/poly(methyl methacrylate)

The use of methyl methacrylate/poly(methyl methacrylate) as a medium for the exfoliation of graphite platelets without any chemical treatment is reported. The dispersions, characterized by transmission electron microscopy and Raman spectroscopy, confirmed the obtainment of graphene sheets a few layers thick. We found that the electrical conductivity of such nanocomposites can be activated at temperature by the application of an external electric field, this effect being reversible after removal of the thermal stimulus. This result provides an initial understanding of how electric field assisted thermal annealing can be used to control the bulk physical properties of such composites. Copyright © 2012 Society of Chemical Industry     

Novel synthesis of poly(methyl methacrylate) brush encapsulated silica particles

Silica (SiO₂)‐crosslinked polystyrene (PS) particles possessing photofunctional N,N‐diethyldithiocarbamate (DC) groups on their surface were prepared by the free‐radical emulsion copolymerization of a mixture of SiO₂ (diameter = 20 nm), styrene, divinyl benzene, 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC), and 2‐hydroxyethyl methacrylate with a radical initiator under UV irradiation. In this copolymerization, the inimer VBDC had the formation of a hyperbranched structure by a living radical mechanism. The particle sizes of such core–shell structures [number‐average particle diameter (D_n) = 35–40 nm] were controlled by the variation of the feed amounts of the monomers and surfactant, or emulsion system. The size distributions were relatively narrow (weight‐average particle diameter/D_n ≈ 1.05). These particles had DC groups on their surface. Subsequently, poly(methyl methacrylate) brush encapsulated SiO₂ particles were synthesized by the grafting from a photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by SiO₂‐crosslinked PS particles as a macroinitiator. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子的制备

由种子乳液聚合法制备了聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子。以过硫酸钾(KPS)为引发剂,辛基酚聚氧乙烯醚(OP-10)为乳化剂,合成了聚苯乙烯(PS)种子核;连续滴加甲基丙烯酸甲酯(MMA),在核表面富集MMA,制备了粒径范围在0.16~0.67μm的核-壳粒子;当单体苯乙烯与甲基丙烯酸甲酯(St/MMA)的比为30∶70(质量比)时,所得粒径在0.18μm,粒径分布为0.012。差示扫描量热(DSC)研究显示,复合粒子的玻璃化转变温度(Tg)为97.2℃,峰形单一,表现出良好的热性能。     

High-pressure sorption of carbon dioxide in solvent-cast poly(methyl methacrylate) and poly(ethyl methacrylate) films

Carbon dioxide sorption isotherms in poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) are reported for pressures up to 20 atm. Temperatures between 35 and 80°C were studied for PMMA and temperatures between 30 and 55°C were studied for PEMA. Typical dual mode sorption isotherms concave to the pressure axis were observed in all cases. The measured Langmuir sorption capacities of both polymers extrapolated to zero at the glass transition (T_g) consistent with the behavior of other glassy polymer/gas systems. Sorption enthalpies for CO₂ in the Henry's law mode for PMMA and PEMA are in the same range (?2 to ?4 kcal/mole) as has been reported for a variety of other glassy polymers such as poly(ethylene terephthalate), polycarbonate, and polyacrylonitrile. Some of the data suggest that postcasting treatment of the PEMA films left a small amount of residual solvent in the film. the presence of the trace residual solvent during quenching from the rubbery to the glassy state after annealing appears to cause a dilation of the Langmuir capacity and an alteration in the apparent Langmuir affinity constant of the PEMA film. These results suggest the possibility of tailoring physical properties of glassy polymers such as sorptivity, permeability, impact strength, and craze resistance by doping small amounts of selected residuals into polymers prior to quenching to the glassy state from the rubbery state.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Branched methyl methacrylate copolymer particles prepared by RAFT dispersion polymerization

Reversible addition–fragmentation chain transfer (RAFT) dispersion copolymerization of methyl methacrylate (MMA) and tripropylene glycol diacrylate (TPGDA) was carried out in ethanol/water in the present work. S-1-Dodecyl-S′-(α,α-dimethyl-α″-aceticacid) trithiocarbonate (TTC) was used as a chain transfer agent to inhibit the occurrence of gelation. Branched poly(methyl methacrylate) (PMMA) particles with a very narrow size distribution was prepared by a two-stage method: the addition of a RAFT agent and a TPGDA agent to the system followed the nucleation stage. The particles had an average diameter within 1.9–2.7 μm and size distribution of 1.12–1.24. Molecular weight, molecular weight distribution, compositions and structure of copolymer were investigated by GPC and 1H NMR characterization. The GPC curves showed a bimodal distribution, indicating that MMA homopolymer was synthesised during the nucleation stage. In addition, 1H-NMR proved that MMA and TPGDA branched copolymer was synthesised after the nucleation stage. TPGDA fraction in the copolymer was lower than that in the initial monomer. It was determined that the intrinsic viscosity of the copolymer decreased with conversion and the Mark–Houwink exponent α of copolymer was reduced from 0.643 to 0.548, which further confirmed the branched structure of the copolymer.     

Preparation of monodisperse poly(methyl methacrylate) particles by radiation-induced dispersion polymerization using vinyl terminus polysiloxane macromonomer as a polymerizable stabilizer

Monodisperse poly(methyl methacrylate) particles were prepared directly by radiation-induced dispersion polymerization in hexane-ethanol media using vinyl terminus polysiloxane (PSI) macromonmer as a polymerizable stabilizer at room temperature. This method takes advantage of the specialties of radiation-induction, which may result in the formation of uniform polymer particles. The gel effect is evident from the polymerization kinetics curves. Vinyl terminus PSI macromonomer acted as not only a comonomer, but also as a stabilizer. The characterization of PMMA particles was carried out by the scanning electron microscope (SEM), FT-IR, ¹H-NMR and X-ray photoelectron spectroscope (XPS). XPS results show that the graft PSI macromonomers were anchored on the surface of PMMA particles to provide a steric stabilization to the PMMA particles.     

An experimental and theoretical investigation of the compressive properties of multi-walled carbon nanotube/poly(methyl methacrylate) nanocomposite foams

Polymer nanocomposite foams are promising low density substitutes for nanocomposites. Carbon nanotube/polymer nanocomposite foams possess high strength, low density, and can be made conductive. Good control of foam properties is of great importance in the application of such materials. In the current study, multi-walled carbon nanotubes (MWNTs) with controlled aspect ratio were used to alter the foam morphology in MWNT/poly(methyl methacrylate) (PMMA) nanocomposite foams produced by a supercritical carbon dioxide (CO₂) foaming process. It was found that with the addition of one weight percent of MWNTs, the Young’s modulus of polymer foams increased by as much as 82%, and the collapse strength increased by as much as 104%. The influence of MWNT aspect ratio on the compressive properties of nanocomposite foams was investigated. The addition of MWNTs influenced the foam properties in two ways: improving the compressive properties of the solid matrix, and reducing the bubble size of the nanocomposite foams. A modified constitutive model for predicting the compressive properties of high density closed-cell polymer foams was developed. The influence of the bubble size on the mechanical properties of polymer foams was discussed based on the new model.     

Film formation of poly (methyl methacrylate) latex with pyrene functional poly (divinylbenzene) microspheres prepared by click chemistry

This work reports on the application of steady state fluorescence (SSF) technique for studying film formation from poly(methyl methacrylate) (PMMA) latex and poly(divinylbenzene) (PDVB) microsphere composites. Pyrene (P) functionalized PDVB cross‐linked spherical microspheres with diameters of 2.5 μm were synthesized by using precipitation polymerization technique followed by click coupling reaction. The diameter of the PMMA particles prepared by emulsion polymerization were in the range of 0.5–0.7 μm. PMMA/PDVB composite films were then prepared by physically blending of PMMA latex with PDVB microspheres at various composition (0, 1, 3, 5, 10, 20, 40, and 60 wt%). After drying, films were annealed at elevated temperatures above T_g of PMMA ranging from 100 to 270°C for 10 min time intervals. Evolution of transparency of the composite films was monitored by using photon transmission intensity, I_tr. Monomer (I_P) and excimer (I_E) fluorescence intensities from P were measured after each annealing step. The possibility of using the excimer‐to‐monomer intensity ratio (I_E/I_P) from PDVB microparticles as a measure of PMMA latex coalescence was demonstrated. Diffusion of the PMMA chains across the particle–particle interfaces dilutes the dyes, increasing their separation. The film formation stages of PMMA latexes were modeled by monitoring the I_E/I_P ratios and related activation energies were determined. There was no observable change in activation energies confirming that film formation behavior is not affected by varying the PDVB composition in the studied range. SEM images of PMMA/PDVB composites confirmed that the PMMA particles undergo complete coalescence forming a continuous phase in where PDVB microspheres are dispersed. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

The transport of methyl methacrylate monomer in poly(methyl methacrylate)

The absorption kinetics and equlibria of methyl methacrylate monomer into poly(methyl methacrylate) were studied over a range of penetrant activities. The interval sorption kinetics at elevated activities were determined, compared, and contrasted with the integral sorption experiments in previously unpenetrated film samples. The sorption kinetics in previously unpenetrated films were predominantly case II or relaxation controlled at high activities. A Fickian contribution to the overall kinetics was apparent at lower activities. In contrast, interval sorption, at elevated activities in previously equilibrated and plasticized samples, followed Fickian kinetics rather closely, whereas resorption, over an activity range which involved a traversal of the effective T_g, was characterized by more complicated kinetics involving a super case II mechanism at long times. These composite results reinforce the notion that the kinetics describing penetration of a single penetrant into a single polymer are extremely sensitive to the boundary condition imposed upon the polymeric sorbent.     

Modification of pristine multiwalled carbon nanotube by grafting with poly(methyl methacrylate) using benzoyl peroxide initiator

Multiwalled carbon nanotube was successfully grafted with poly(methyl methacrylate) by free radical mechanism using benzoyl peroxide initiator. The reaction was carried out in situ, where the initiator and methyl methacrylate monomer generated the polymer‐free radical that was subsequently grafted to the surface of the pristine multiwalled carbon nanotube. The multiwalled carbon nanotube grafted poly(methyl methacrylate) (MWCNT‐g‐PMMA) were characterized using Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, ¹³ C‐solid NMR spectroscopy, X‐ray photoelectron spectroscopy, and scan electron microscopy. From the result of the characterizations, the grafting of poly(methyl methacrylate) on to multiwalled carbon nanotube was confirmed, and a percentage grafting of 41.51% weight was achieved under optimized conditions with respect to the temperature and the amount of the initiator. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43270.     

Mechanical properties of drawn poly(methyl methacrylate) filled with ultrafine particles

The elastic and yield properties of drawn poly(methyl methacrylate) (PMMA) filled with ultrafine SiO₂ are described as functions of filler content and size. The drawn PMMA composites were made by uniaxially drawing to x4.0 at 100°C and at a rate of 20 mm/min. Four compliance values, i.e., S₃₃, S₁₁, S₁₃, and S₄₄ were determined. These values decreased with filler content and decreasing filler size. The relative compliance values S^de/S^do(S^de is the compliance of drawn PMMA composites and S^do is that of drawn unfilled PMMA) are almost equivalently changed with changes in filler content. The elastic properties of drawn PMMA composites are thus reinforced isotopically. This is characteristic of PMMA which has a large side group. The yield behavior of drawn PMMA composites have similar filler size and content dependence to those of elastic properties except that the transverse yield stresses become more brittle with filler content. The anisotropy in yield stress is relatively larger than that of elastic properties. This is probably because the anti-reiforcing effect, such as fibrillation becomes prominent with increasing filler content in the perpendicular direction.     

Optimum strength of composites of ceramic particles in poly(methyl methacrylate)

Ceramic particles were sedimented in methyl methacrylate, which was then polymerized by exposre to γ-rays. After annealing, specimens were cut and tested, and the ceramic content determined by ashing. Diamond indentation hardness was found to increase monotonically with increase in ceramic content. In contrast, both Young's modulus and, more markedly, flexural strength were found to give optimum (peak) values for a content of lithium aluminum silicate near 80 wt-percent. The higher silicate contents were reached with use of a silane coupling agent and by centrifuging, prior to polymerization. Examination of fracture surfaces by scanning electron microscopy indicated that the decrease in mechanical properties was due to the presence of voids in the polymeric matrix. It is suggested that void formation becomes serious when ceramic particles are initially too close-packed to respond to conraction, during polymerization, by shifting closer together. Consistent with this suggestion, both void formation and peaking in strength can be prevented by continuously centrifuging the composite throughout the polymerization reaction.     

A new technique for foaming submicron size poly(methyl methacrylate) particles

About 0.7–2 μm diameter poly (methyl methacrylate) (PMMA) foamed particles were prepared via thermally induced phase separation (TIPS) from a PMMA/ethanol mixture and vacuum dried. It was found that ethanol, known to be a poor solvent to PMMA, could dissolve PMMA when the temperature was over 60°C. The solubility of PMMA (M_w = 15,000 and M_w = 120,000) in ethanol was measured and was found to increase as the temperature increased. PMMA particles on the scale of submicron and single micron diameter could be precipitated from the PMMA/ethanol solution by temperature quenching. Then, since the precipitated particles contained a certain amount of ethanol, the precipitated particles could be foamed using the ethanol as a foaming agent in a vacuum drying process. Vacuum drying at temperatures slightly below the glass transition temperature of the polymer could make the particles foam. The effects of foaming temperature and the molecular weight of the polymer on the size of foamed particles were investigated. The experimental results showed that the vapor pressure and the molecular weight of the polymer are key factors determining the expandability of the micro particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007